KR20140137307A - Coloring composition, colored cured film and display device - Google Patents

Abstract

An object of the present invention is to provide a coloring composition suitable for formation of a colored cured film having high contrast. To achieve the object, provided is a coloring composition including: (A) a coloring agent; (B) a binder resin; and (C) a polymeric compound, wherein, the coloring agent includes a salt of a cation having a xanthenes backbone or a cation having a methine backbone and an anion of a metal complex, and a metal to form the metal complex is at least one selected from the group consisting of iron, nickel, copper, and aluminum.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored composition, a colored cured film,

The present invention relates to a colored composition, a colored cured film and a display device, and more particularly to a colored curable film used for a transmissive or reflective color liquid crystal display device, a solid-state image sensor, an organic EL display device, , A colored cured film formed using the colored composition, and a display element comprising the colored cured film.

When a color filter is manufactured using a coloring and radiation-sensitive composition, a pigment-dispersed coloring and radiation-sensitive composition is applied onto a substrate and dried, and then the dry film is irradiated with a desired pattern (hereinafter, (For example, refer to Patent Documents 1 and 2) are known. A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (see, for example, Patent Document 3) is also known. There is also known a method of obtaining pixels of respective colors by an ink jet method using a pigment dispersion type colored resin composition (see, for example, Patent Document 4).

However, it is known that it is effective to use a dye as a coloring agent in order to achieve high luminance and high color purity of a display element or high-definition of a solid-state image pickup element. For example, a xanthene compound (for example, ) Or a polymethine compound (see, for example, Patent Document 6).

Japanese Patent Application Laid-Open No. 2-144502 Japanese Patent Laid-Open Publication No. 3-53201 Japanese Patent Application Laid-Open No. 6-35188 Japanese Patent Application Laid-Open No. 2000-310706 Japanese Patent Application Laid-Open No. 2011-138094 Japanese Patent Application Laid-Open No. 2009-235392

However, since the xanthene compound or the polymethine compound is a compound emitting fluorescence, there is a problem that when these are used as a colorant, the contrast is lowered. Therefore, even when a dye such as a xanthene compound or a polymethine compound is used as a coloring agent, a coloring composition capable of forming a colored cured film having a high contrast is strongly desired.

Accordingly, it is an object of the present invention to provide a coloring composition suitable for forming a colored cured film having a high contrast. Another object of the present invention is to provide a colored cured film formed using the colored composition and a display device comprising the colored cured film.

As a result of extensive studies, the present inventors have found that the above problems can be solved by using a colorant having a specific structure.

That is, the present invention relates to a colored composition comprising (A) a colorant, (B) a binder resin and (C) a polymerizable compound,

Wherein the colorant comprises a salt of a cation having a xanthene skeleton or a cation having a methine skeleton and an anion of a metal complex,

Wherein the metal constituting the metal complex is at least one selected from the group consisting of iron, nickel, copper and aluminum.

The present invention also provides a display element comprising a colored cured film formed using the colored composition and the colored cured film. Here, the term "colored cured film" means each color pixel, a black matrix, a black spacer, etc. used in a display element or a solid-state image pickup element.

By using the coloring composition of the present invention, a colored cured film having high contrast can be formed.

Accordingly, the coloring composition of the present invention can be suitably used for the production of solid-state image pickup devices such as color liquid crystal display devices, organic EL display devices, display devices such as electronic paper, and CMOS image sensors.

Hereinafter, the present invention will be described in detail.

Coloring composition

Hereinafter, the constituent components of the coloring composition of the present invention will be described in detail.

- (A) Colorant -

The coloring composition of the present invention contains (A) a salt with a cation having a cationic skeleton or a methine skeleton as a colorant and a salt with an anion of a metal complex, and the metal constituting the metal complex is selected from the group consisting of iron, Copper, and aluminum. Hereinafter, this salt is also referred to as " present coloring agent ".

As the cation having a xanthene skeleton, a cation represented by the following formula (1) is preferable.

[In the formula (1)

R ^1, R ^2, R ³ and R ⁴ are independently a hydrogen atom, -R ⁸ or a carbon number of 6 to 10 are shown a group of the aromatic hydrocarbon, the hydrogen atoms contained only the aromatic hydrocarbon groups include a halogen atom, -R ⁸ each other, -OH, -OR ⁸ , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ R ⁸ , -SO ₂ NHR ⁹ or -SO ₂ NR ⁹ R ¹⁰ There may be,

R ⁵ and R ⁶ independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

R ⁷ represents -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ R ⁸ , -SO ₂ NHR ⁹ or -SO ₂ NR ⁹ R ¹⁰ ,

r represents an integer of 0 to 5, and when r is an integer of 2 or more, plural R ^{7 s} may be the same or different,

R ⁸ represents a saturated hydrocarbon group having 1 to 20 carbon atoms, provided that the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and an oxygen atom, a carbonyl group or -NR ⁸ - may be interposed between the CC bonds of the saturated hydrocarbon group Lt; / RTI >

R ⁹ and R ¹⁰ independently represent a straight chain alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Z, or a substituted or unsubstituted C 2 -C 10 arylene group formed by bonding R ⁹ and R ¹⁰ to each other. Provided that the hydrogen atoms contained in the alkyl group and the cycloalkyl group may be substituted with a hydroxyl group, a halogen atom, -Z, -CH = CH _2, or -CH = CHR ₈ , May have an oxygen atom, a carbonyl group or -NR ⁸ - between the CC bonds of the cycloalkyl group, and the hydrogen atom contained in the heterocyclic group may be substituted with -R ⁸ , -OH or -Z,

M represents a sodium atom or a potassium atom,

Z represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 4 to 10 carbon atoms, provided that the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is -OH, -R ⁸ , -OR ⁸ , - NO ₂ , -CH = CH ₂ , -CH = CHR ^8, or may be substituted with a halogen atom)

The saturated hydrocarbon group in R ⁸ may be any of linear, branched and cyclic, and may have a crosslinked structure when the number of carbon atoms is 1 to 20. Specific examples thereof include a saturated aliphatic hydrocarbon group and a saturated alicyclic hydrocarbon group. Examples of the saturated aliphatic hydrocarbon group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, A hexadecyl group, a hexadecyl group, a hexadecyl group, a hexadecyl group, a heptadecyl group, a hexadecyl group, a heptadecyl group, a hexadecyl group, And an octadecyl group. Examples of the saturated alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a t-butylcyclohexyl group, a cycloheptyl group and a cyclooctyl group; A condensed polycyclic hydrocarbon group such as a tricyclodecanyl group, a decahydro-2-naphthyl group, and an adamantyl group. Examples of the group having an oxygen atom between the CC bonds of the saturated hydrocarbon group include a methoxypropyl group, an ethoxypropyl group, a 2-ethylhexyloxypropyl group, and a methoxyhexyl group. Among them, as the saturated hydrocarbon group for R ⁸ , a straight or branched alkyl group having 1 to 10 carbon atoms is preferable, and a straight-chain or branched alkyl group having 1 to 6 carbon atoms is more preferable.

Examples of the straight chain alkyl group having 1 to 20 carbon atoms and the cycloalkyl group having 3 to 30 carbon atoms in R ⁹ and R ¹⁰ include the same groups as described above. Among them, as R ⁹ and R ¹⁰ , a linear or branched alkyl group having 6 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms are preferable.

The substituted or unsubstituted heterocyclic group having 2 to 10 carbon atoms formed by bonding R ⁹ and R ¹⁰ to each other may be a monocyclic heterocyclic group, a polycyclic heterocyclic group, or an unsaturated ring or a saturated ring. Specific examples thereof include a pyrrolyl group, a pyridyl group, an indolyl group, an isoindolyl group, a quinolyl group, an isoquinolyl group, a carbazolyl group, a phenanthridinyl group, an acridinyl group, a furanyl group, An isobenzofuranyl group, an isochromanyl group, a xanthanyl group, a thiophenyl group, a thienthrenyl group, a phenoxathiinyl group, and a phenothiazinyl group. Examples of the substituent in the heterocyclic group include a halo group, a hydroxyl group, an alkoxy group, an amino group, and an alkyl group. Examples of the aromatic heterocyclic group having 4 to 10 carbon atoms in Z include furyl, thienyl, pyridyl, pyrrolyl, oxazolyl, isoxazole, thiazolyl, isothiazolyl, A pyrazolyl group, and a pyrimidyl group.

Examples of the aromatic hydrocarbon group in R ¹ , R ² , R ³ , R ⁴ and Z include a phenyl group and a naphthyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The -OR ⁸ in R ¹ , R ² , R ³ and R ⁴ is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, such as methoxy group, ethoxy group, n- Alkoxy groups such as propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, , Ethoxyethoxy group, and the like.

Examples of -SO ₃ R ^{8 in} R ¹ , R ² , R ³ , R ⁴ and R ⁷ include a methanesulfonyl group, an ethanesulfonyl group, a hexanesulfonyl group and a decanesulfonyl group. Examples of -CO ₂ R ⁸ include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, a butyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a methoxypropyloxycarbonyl group. Examples of R ⁹ and R ^{10 in} -SO ₂ NHR ⁹ and -SO ₂ NR ⁹ R ¹⁰ include a branched alkyl group having 6 to 8 carbon atoms, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, an allyl group, An aralkyl group having 2 to 8 carbon atoms, a hydroxyl group substituted alkyl group having 2 to 8 carbon atoms, an alkyl group having 2 to 8 carbon atoms having an oxygen atom between the CC bonds, and an aryl group having 6 to 10 carbon atoms.

The alkyl group having 1 to 8 carbon atoms in R ⁵ and R ⁶ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be a straight chain or branched chain.

Representative examples of the cations represented by the above formula (1) include, for example, cations represented by the following formulas.

As the cation having a methine skeleton, a cation represented by the following formula (2) or (3) is preferable.

[In the formula (2)

R ²¹ to R ²⁶ independently represent a hydrogen atom or an alkyl group,

The ring Z ¹ and Z ² independently represent an aromatic ring, and the hydrogen atom contained in the aromatic ring may be a halogen atom, a nitro group, an alkyl group having 1 to 8 carbon atoms, a fluorinated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms , An alkylcarbonyl group having 2 to 6 carbon atoms,

and g represents an integer of 1 to 4)

[In the formula (3)

R ²⁷ to R ³⁰ independently represent a hydrogen atom or an alkyl group,

The ring Z ³ and Z ⁴ independently represent an aromatic ring, and the hydrogen atom contained in the aromatic ring may be a halogen atom, a nitro group, an alkyl group having 1 to 8 carbon atoms, a fluorinated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms , An alkylcarbonyl group having 2 to 6 carbon atoms,

Q represents an oxygen atom or a sulfur atom,

h represents an integer of 1 to 4]

The alkyl group in R ²¹ to R ³⁰ is preferably an alkyl group having 1 to 8 carbon atoms, further preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include the same ones as described above.

As the aromatic ring in the rings Z ¹ to Z ⁴ , an aromatic ring having 6 to 10 carbon atoms is preferable, and a benzene ring and a naphthalene ring are more preferable. The aromatic ring may be substituted with a halogen atom, a nitro group, an alkyl group having 1 to 8 carbon atoms, an alkyl fluoride group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. Examples of the halogen atom, the alkyl group having 1 to 8 carbon atoms, and the alkoxy group having 1 to 6 carbon atoms include the same ones as described above. The fluorinated alkyl group having 1 to 8 carbon atoms is preferably a fluorinated alkyl group having 1 to 4 carbon atoms. Specific examples thereof include those in which a part or all of the hydrogen atoms of the above-mentioned alkyl group are substituted with a fluorine atom, and a perfluoroalkyl group is particularly preferable. The aromatic ring may be substituted with an alkylcarbonyl group having 2 to 6 carbon atoms, and the alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 5 carbon atoms. Specific examples thereof include an acetyl group, a propionyl group, a butyryl group, and a valeryl group.

g and h are preferably 1 or 2.

As typical examples of the cation represented by the above formula (2), for example, a cation represented by the following formula may be mentioned.

Typical examples of the cation represented by the above formula (3) include, for example, cations represented by the following formulas.

Next, anions of metal complexes will be described.

The anion of the metal complex is not particularly limited, but an anion of a metal complex having an azo compound in a ligand is preferable. Here, the azo compound is a generic name of a compound having at least one azo group in the molecule. Examples of such a ligand include a ligand represented by the following formula (a).

[In the formula (a)

The ring Z < ⁵ > independently represents a substituted or unsubstituted heterocyclic group,

The ring Z ⁶ represents an aromatic hydrocarbon group which is substituted or unsubstituted independently of each other,

t ¹ and t ² independently represent 0 or 1]

In the present invention, specific examples of the anions of the metal complex having an azo compound in the ligand include anions represented by the following formula (4).

[In the formula (4)

The ring Z < ⁵ > independently represents a substituted or unsubstituted heterocyclic group,

The ring Z ⁶ represents an aromatic hydrocarbon group which is substituted or unsubstituted independently of each other,

M ¹ represents iron, nickel, copper or aluminum,

t ¹ and t ² independently represent 0 or 1]

The heterocyclic group in ring Z ⁵ may be a monocyclic heterocyclic group or a polycyclic heterocyclic group. As such a heterocyclic group, a monovalent heterocyclic group having 3 to 10 carbon atoms is preferable, and specific examples thereof include a pyrrolidinyl group, an imidazolidinyl group, a pyrazolidinyl group, a morpholinyl group, a thiomorpholinyl group, a piperidyl group, A nitrogen-containing alicyclic heterocyclic group such as a lidino group, a piperazinyl group and a homopiperazinyl group, other alicyclic heterocyclic groups such as a 1,3-dioxolan-2-yl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group , A pyridazinyl group, a quinolyl group, an isoquinolyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, an imidazolyl group, a pyrazolyl group, a triazoyl group, a tetrazolyl group, Nitrogen-containing aromatic heterocyclic groups such as a benzothiazolyl group, an oxazolyl group, an indolyl group, an indazolyl group, a benzoimidazolyl group and a phthalimide group, other aromatic heterocyclic groups such as thienyl group, furyl group, pyranyl group, Ventilation. Among them, a nitrogen-containing aromatic heterocyclic group is preferable, and a pyridyl group and a pyrazolyl group are more preferable.

Such a heterocyclic group may further have a substituent within a range not deviating from the present invention. The position and the number of the substituent are arbitrary, and when two or more substituents are present, the substituents may be the same or different. Examples of the substituent include a halogen atom, a hydroxyl group, a cyano group, a formyl group, a carboxyl group, a nitro group, an amino group, a dialkylamino group, a diarylamino group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, A trialkylsilyl group, a mercapto group, an allyl group, an alkylsulfonyl group, an alkylsulfamoyl group, an aliphatic hydrocarbon group, and an aromatic hydrocarbon group. These substituents may further have a substituent. Among them, the substituent of the heterocyclic group is preferably a hydroxyl group, a cyano group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

Examples of the aliphatic hydrocarbon group include an unsaturated aliphatic hydrocarbon group such as an alkenyl group and an alkynyl group in addition to the saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms described in the formula (1). The alkenyl group is preferably an alkenyl group having 2 to 16 carbon atoms, and examples thereof include an ethynyl group, a 1-propenyl group, a 1-butenyl group, a 1-butadienyl group, (2-ethyl-2-butenyl group, 2-octenyl group, (4-ethenyl) -5-hexenyl group and 2-decenyl group. The alkynyl group is preferably an alkynyl group having 2 to 12 carbon atoms, and examples thereof include an ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 3-pentynyl group, 1-hexynyl group, -Butynyl group, 2-octynyl group, (4-ethynyl) -5-hexynyl group, 2-decynyl group and the like. The aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. Specific examples of the aromatic hydrocarbon group include monocyclic to tricyclic aromatic hydrocarbon groups having 6 to 14 carbon atoms such as phenyl, naphthyl, anthryl, phenanthryl, azulenyl, and 9-fluorenyl groups.

The aromatic hydrocarbon group in the ring Z ⁶ preferably has 6 to 20 carbon atoms and more preferably 6 to 10 carbon atoms. Specific examples include the same ones as described above. Of these, a phenyl group is preferable. Examples of the substituent of the aromatic hydrocarbon group include, in addition to those exemplified in the explanation of the heterocyclic group in the ring Z ⁵ , a group in which a sulfo group, sulfamoyl group, alkylamide group, two alkylamide groups are bonded, (Hereinafter simply referred to as " a group in which two alkylamide groups are bonded ") bonded to the amide group of the other alkylamide group. Among them, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, a sulfo group, an alkylsulfonyl group, a sulfamoyl group, an alkylsulfamoyl group, an alkylamido group, a group in which two alkylamido groups are bonded and an aliphatic hydrocarbon group desirable. The alkyl moiety of the alkylsulfonyl group, the sulfamoyl group and the alkyl sulfamoyl group, and the aliphatic hydrocarbon group may further have a substituent.

The anion represented by the formula (4) is preferably an anion represented by the following formula (4-1) or (4-2).

[In the formula (4-1), "

R ⁴¹ independently represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms,

R ⁴² is independently an alkyl group having 1 to 8 carbon atoms, a halogen atom, a nitro group, -SO ₃ H, -SO ₂ R ⁴⁴ , -SO ₂ NH ₂ , -SO ₂ NHR ⁴⁵ or -NHCO-R ⁴⁶ -NHCOR ⁴⁷ Lt; / RTI >

R ⁴³ independently represent a nitro group, -SO ₃ H, -SO ₂ NH ₂ or -SO ₂ NHR ⁴⁸ ,

R ⁴⁴ , R ⁴⁵ , R ⁴⁷ and R ⁴⁸ independently represent a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms,

R ⁴⁶ represents an alkanediyl group having 1 to 6 carbon atoms,

M ² represents iron, nickel, copper or aluminum,

p and q independently represent an integer of 0 to 2,

t ² independently represent 0 or 1]

In the formula (4-2)

R ⁵¹ independently represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms,

R ⁵² independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a sulfo group, -SO ₂ NHR ⁵⁴ or -NHCOR ⁵⁵ ,

R ⁵³ independently represents an alkyl group having 1 to 8 carbon atoms or a cyano group,

R ⁵⁴ and R ⁵⁵ independently represent an alkyl group having 1 to 8 carbon atoms,

M ³ represents iron, nickel, copper or aluminum,

x and y independently represent an integer of 0 to 2,

t ² independently represent 0 or 1]

The alkyl group having 1 to 8 carbon atoms in R ⁴¹ , R ⁴² , R ⁴⁴ , R ⁴⁵ , R ⁴⁷ , R ⁴⁸ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ may be a straight chain or branched chain, Specific examples thereof include the same ones as described above. Among them, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.

Examples of the substituent of the alkyl group in R ⁴¹ include a hydroxyl group and -COOR ⁴⁹ . R ⁴⁹ is an alkyl group having 1 to 8 carbon atoms, and may be a straight chain or branched chain.

Examples of the substituent of the alkyl group in R ⁴⁴ , R ⁴⁵ , R ⁴⁷ and R ⁴⁸ include an alkoxy group having 1 to 6 carbon atoms.

Examples of the substituent of the alkyl group in R ⁵¹ include a hydroxyl group, -COOR ⁵⁶ , -OCOR ⁵⁶ , -CO-R ⁵⁷ -OH, -COR ⁵⁶ and -CONHR ⁵⁸ . R ⁵⁶ and R ⁵⁸ independently represent an alkyl group having 1 to 8 carbon atoms or a phenyl group, and the alkyl group may be a straight chain or branched chain. R ⁵⁷ is an alkanediyl group having 1 to 6 carbon atoms, and may be a straight chain or branched chain. Specific examples of the alkanediyl group having 1 to 6 carbon atoms include a methylene group, an ethylene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, A butane-1,3-diyl group, a butane-1, 4-diyl group, a pentane-1, 4-diyl group, a pentane-1,2-diyl group, -1,5-diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group and the like.

The alkanediyl group having 1 to 6 carbon atoms in R ⁴⁶ may be a straight chain or branched chain.

M ² and M ³ are preferably iron, nickel or copper, more preferably iron and nickel, and more preferably iron.

p is preferably 0 or 1.

q is preferably 1 or 2.

x is preferably 0 or 1.

y is preferably 2, and in this case, two R ⁵³ on the heterocyclic ring may be the same, but are preferably different.

The present colorant may be obtained by a salt exchange reaction between a compound containing a cation having a xanthene skeleton or a cation containing a methine skeleton and a compound containing an anion of a metal complex.

As the compound containing a cation having a xanthene skeleton, known xanthene basic dyes can be used, and examples thereof include xanthene basic dyes such as CI Basic Violet 11 and Rhodamine 6G. Of these, rhodamine 6G is preferred.

Examples of the compound containing a cation having a methine skeleton include CI basic red 12, CI basic red 13, CI basic red 14, CI basic violet 7, CI basic violet 16, Based basic dyes such as CI Basic Yellow 1, CI Basic Yellow 11, CI Basic Yellow 13, CI Basic Yellow 21, CI Basic Yellow 28, CI Basic Yellow 51, and the like. Among them, C.I. Basic Red 12, C.I. Basic Red 13 and C.I. Basic Red 14 are preferable.

In the present invention, the term " basic dye " means an ionic dye in which the cation unit is a chromophore, and an ionic dye forming a salt with the cation unit is also a basic dye.

The compound containing an anion of a metal complex having an azo compound in a ligand in a compound containing an anion of a metal complex can be obtained by reacting an azo compound synthesized by the method described in, for example, Japanese Patent Laid-Open Publication No. 2011-148993, Nickel, copper, or aluminum.

The coloring composition of the present invention may be mixed with other coloring agents other than the present coloring agent. No particular limitation is imposed on the other colorants, and the color and the material can be appropriately selected according to the use. Any of pigments, dyes and natural pigments other than the present colorant can be used, but in the meaning of obtaining pixels with high luminance and color purity Organic pigments and organic dyes are preferable, and organic pigments are more preferable.

Examples of the organic pigments include pigments classified as pigments in a color index (CI, published by The Society of Dyers and Colourists). Among them, JP-A-2001-081348, JP-A- Japanese Patent Application Laid-Open Nos. 2010-026334, 2010-191304, 2010-237384, 2010-237569, 2011-006602, Japanese Patent CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 7, CI Pigment Red 7, CI Pigment Red 244, CI Pigment Blue 15: 6, CI Pigment Blue 80, CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 15, The yellow bit 180, other than the organic pigment lake pigments such as C.I. Pigment Yellow 211, C.I. Pigment Orange 38, C.I. Pigment Violet 23 is preferred. Among the lake pigments, triarylmethane lake pigments, xanthane lake pigments and azo lake pigments are preferable, and triarylmethane lake pigments and xanthane lake pigments are more preferable.

Examples of the organic dyes include xanthene dyes, triarylmethane dyes, methine dyes, anthraquinone dyes, and azo dyes. Xanthan dyes having no anion of a metal complex, anions of a metal complex Methine-based dyestuffs which do not contain a dye are more preferable. More specifically, Japanese Patent Application Laid-Open Nos. 2010-32999, 2010-254964, 2011-138094, 10/123071, 2011- Organic dyes described in Japanese Patent Application Laid-Open No. 116803, Japanese Patent Application Laid-Open No. 2011-117995, Japanese Patent Application Laid-Open No. 2011-133844, Japanese Patent Laid-Open No. 2011-174987, and the like.

In the present invention, the pigment and the dye may be used alone or in combination of two or more.

When a pigment is used as another colorant in the present invention, the pigment may be purified and used by recrystallization, reprecipitation, solvent cleaning, sublimation, vacuum heating, or a combination thereof. Further, the pigment may be used by modifying its particle surface with a resin as necessary. As the resin for modifying the particle surface of the pigment, for example, a vehicle resin disclosed in Japanese Patent Application Laid-Open No. 2001-108817 or a commercially available resin for dispersing various pigments may be mentioned. Examples of the resin coating method for the carbon black surface include a method described in Japanese Patent Application Laid-Open No. 9-71733, Japanese Patent Application Laid-Open No. 9-95625, Japanese Patent Application Laid-Open No. 9-124969 Can be adopted. Further, the organic pigment may be used by finely grinding primary particles by so-called salt milling. As a method of the salt milling, for example, a method disclosed in Japanese Unexamined Patent Application Publication No. 08-179111 can be adopted.

Further, in the present invention, known dispersants and dispersion auxiliaries may be further contained in combination with other colorants to be arbitrarily mixed. Examples of the known dispersant include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene alkyl phenyl ether-based dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester- A dispersant, and an acrylic dispersant. Examples of the dispersing aid include a pigment derivative and the like.

Such dispersants are commercially available and include, for example, acrylic dispersants such as Disperbyk-2000, Disperby-2001, BYK-LPN6919, BYK-LPN21116 and BYK-LPN21324 (manufactured by BYK- Disperic-162, Disperobic-165, Disperobic-167, Disperobic-170 and Disperic-182 (manufactured by BYK), Sorbus 76500 (Manufactured by Lubrizol Co., Ltd.) as a polyethyleneimine-based dispersant, such as Sorbus 24000 (manufactured by Lubrizol Corporation), and a polyester dispersant such as Ajisper PB821, Ajisper PB822, Ajisper PB880, Spur PB881 (manufactured by Ajinomoto Fine Techno Co., Ltd.), and the like.

Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

In the present invention, the other colorants may be used alone or in combination of two or more.

When another colorant is used, the content of the present colorant is preferably from 1 to 80% by mass, more preferably from 2 to 50% by mass, still more preferably from 3 to 30% by mass, Particularly preferably 20% by mass.

The content ratio of the (A) coloring agent is usually from 5 to 70% by mass, preferably from 5 to 70% by mass, in terms of forming a black matrix or black spacer having high heat resistance and high brightness and excellent color purity or excellent light- To 60% by mass. Here, the solid content is a component other than the solvent described later.

- (B) Binder Resin -

The binder resin (B) in the present invention is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as a " carboxyl group-containing polymer ") is preferable, and for example, an ethylenically unsaturated monomer having at least one carboxyl group (hereinafter also referred to as " unsaturated monomer (b1) (Hereinafter also referred to as " unsaturated monomer (b2) ").

Examples of the unsaturated monomer (b1) include unsaturated monomers such as (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], omega -carboxylic polycaprolactone mono , p-vinylbenzoic acid, and the like.

These unsaturated monomers (b1) may be used singly or in combination of two or more.

As the unsaturated monomer (b2), for example,

N-substituted maleimide such as N-phenylmaleimide, N-cyclohexylmaleimide;

Aromatic vinyl compounds such as styrene,? -Methylstyrene, p-hydroxystyrene, p-hydroxy-? -Methylstyrene, p-vinylbenzyl glycidyl ether and acenaphthylene;

Acrylates such as methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) (Meth) acrylate, polyethylene glycol (having a degree of polymerization of 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (having a degree of polymerization of 2 to 10) (Meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, propylene glycol Acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) Meth) acrylate, 3,4- (Meth) acrylate esters such as 3-methyl [(meth) acryloyloxymethyl] -3-ethyloxetane, 3 - [(meth) acryloyloxymethyl] oxetane, 3- ;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) Vinyl ethers such as;

And a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane.

These unsaturated monomers (b2) may be used singly or in combination of two or more.

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50 mass%, more preferably 10 to 40 mass%. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

As specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), for example, JP-A-7-140654, JP-A-8-259876, Japanese Patent Laid-Open Nos. 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118 And Japanese Patent Application Laid-Open No. 2004-101728.

Further, in the present invention, for example, Japanese Patent Application Laid-Open No. 5-19467, Japanese Patent Application Laid-Open No. 6-230212, Japanese Patent Application Laid-Open No. 7-207211, (Meth) acryloyl groups such as (meth) acryloyl groups on the side chains as disclosed in JP-A-9-325494, JP-A-11-140144, May be used as the binder resin.

The binder resin in the present invention has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) of usually 1,000 to 100,000, 3,000 to 50,000. By adopting such a shape, the residual film ratio, pattern shape, heat resistance, electric characteristics, and resolution of the coating film are further increased, and occurrence of dry foreign matter at the time of coating can be suppressed to a high level.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. The term "Mn" as used herein refers to the number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a known method. For example, Japanese Unexamined Patent Application Publication No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871 The structure, Mw, and Mw / Mn can also be controlled by the disclosed method.

In the present invention, the binder resins may be used alone or in combination of two or more.

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. By adopting such a form, the alkali developability, the storage stability of the colored composition, and the chromaticity characteristics can be further enhanced.

- (C) Polymerizable compound -

The polymerizable compound in the present invention refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenic unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. As the polymerizable compound in the present invention, a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferable.

Specific examples of the compound having two or more (meth) acryloyl groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, A polyfunctional urethane (meth) acrylate obtained by reacting a (meth) acrylate modified with an alkylene oxide and a polyfunctional (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, a (meth) acrylate having a hydroxyl group and an acid anhydride And a polyfunctional (meth) acrylate having a carboxyl group obtained by the reaction.

Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol; And tri- or higher aliphatic polyhydroxy compounds such as glycerin, trimethylol propane, pentaerythritol and dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate, and glycerol dimethacrylate. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, anhydrous glutaric acid, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, anhydrous pyromellitic acid, biphenyltetracarboxylic acid 2 An anhydride, and a tetrabasic acid dianhydride such as benzophenone tetracarboxylic acid dianhydride.

Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide Trimethylolpropane tri (meth) acrylate modified with at least one member selected from the group consisting of isocyanuric acid tri (meth) acrylate modified with at least one member selected from the group consisting of ethylene oxide and propylene oxide, Pentaerythritol tri (meth) acrylate modified with at least one member selected from propylene oxide, pentaerythritol tetra (meth) acrylate modified with at least one member selected from ethylene oxide and propylene oxide, Dipentaerythritol penta (meth) acrylate modified with at least one member selected from ethylene oxide and propylene oxide Agent) acrylate, ethylene oxide and propylene oxide at least one member of dipentaerythritol hexa (meth modified by selected from) acrylate and the like.

Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. Also, the melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as basic skeletons, and also include melamine, benzoguanamine, or condensates thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ', N', N '', N '' - hexa (alkoxymethyl) Tetra (alkoxymethyl) benzoguanamine, N, N, N ', N'-tetra (alkoxymethyl) glycoluril and the like.

Among these polymerizable compounds, a polyfunctional (meth) acrylate obtained by reacting a tri- or higher valent aliphatic polyhydroxy compound with (meth) acrylic acid, a caprolactone-modified polyfunctional (meth) acrylate, a polyfunctional urethane (meth) (Meth) acrylate having a carboxyl group, N, N, N ', N', N '', N '' - hexa (alkoxymethyl) Alkoxymethyl) benzoguanamine is preferable. Among the multifunctional (meth) acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, Among the polyfunctional (meth) acrylates having a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride, The strength of the colored layer is high and the surface smoothness of the colored layer is excellent and it is difficult to generate background contamination and film residue on the substrate of the unexposed portion and the light shielding layer.

In the present invention, (C) the polymerizable compounds may be used alone or in combination of two or more.

The content of the polymerizable compound (C) in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 700 parts by mass, further preferably 100 to 500 parts by mass, per 100 parts by mass of the (A) colorant. By such a form, curability and alkali developability are further enhanced, and generation of background contamination and film residue on the substrate or on the light shielding layer of the unexposed portion can be suppressed to a high level.

- Photopolymerization initiator -

The coloring composition of the present invention may contain a photopolymerization initiator. Thus, the coloring composition can be imparted with radiation sensitivity. The photopolymerization initiator used in the present invention is a compound which generates active species capable of initiating polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet light, deep ultraviolet light, electron beam, and X-ray.

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an O-acyloxime compound, an onium salt compound, a benzoin compound, a benzophenone compound, Polynuclear quinone compounds, diazo compounds, imidosulfonate compounds and the like.

In the present invention, the photopolymerization initiator may be used alone or in combination of two or more. As the photopolymerization initiator, at least one kind selected from the group consisting of a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, and an O-acyloxime compound is preferable.

Among the preferred photopolymerization initiators in the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone , 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone.

Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- -Morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2' Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

Further, when a nonimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor in combination because the sensitivity can be improved. The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a non-imidazole compound by exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis Ethylamino) benzophenone, and the like. In the present invention, the hydrogen donors may be used singly or in combination of two or more. However, the use of a combination of at least one mercaptan hydrogen donor and at least one amine hydrogen donor may further improve the sensitivity desirable.

Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4 (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) - And triazine compounds having a halomethyl group such as 4,6-bis (trichloromethyl) -s-triazine.

Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O-benzoyloxime), ethanone, 1- [ 1- (9-ethyl-6- (2-methyl-4-tetrahydro-naphthalen- Yl) -, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- { Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -, 1- (O-acetyloxime). As commercially available products of O-acyloxime compounds, NCI-831, NCI-930 (manufactured by ADEKA), DFI-020, DFI-091 (manufactured by Daito Kikusu Kabushiki Kaisha) May be used.

In the present invention, when a photopolymerization initiator other than a non-imidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination. Examples of such sensitizers include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone , Ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino- ) Coumarin, and 4- (diethylamino) chalcone.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, per 100 parts by mass of the (C) polymerizable compound. By adopting this form, the curability and the film property can be further enhanced.

-menstruum-

The coloring composition of the present invention contains the above components (A) to (C) and optionally other components, and is usually prepared as a liquid composition by blending a solvent.

As the solvent, any of the components (A) to (C) and other components constituting the coloring composition may be appropriately selected and used as long as they are dispersible or dissolving, do not react with these components, and have appropriate volatility.

Of these solvents, for example,

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono- -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono- Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol and cyclohexanol;

Ketoalcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, 3-methoxybutyl acetate and 3-methyl-3-methoxybutyl acetate;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Alkoxycarboxylates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate and 3-methyl- Acid esters;

Amyl acetate, n-butyl acetate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, propyl acetate, isopropyl acetate, n- , N-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate;

Aromatic hydrocarbons such as toluene and xylene;

Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, or lactams

And the like.

Among these solvents, (poly) alkylene glycol monoalkyl ethers, lactic acid alkyl esters, (poly) alkylene glycol monoalkyl ether acetates, other ethers, ketones, and the like are preferable from the viewpoints of solubility, pigment dispersibility, Diacetates, alkoxycarboxylic acid esters and other esters are preferable, and propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, Hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3 Butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, Ethyl pyruvate and the like are preferable.

In the present invention, the solvents may be used alone or in admixture of two or more.

Although the content of the solvent is not particularly limited, the total amount of each component excluding the solvent of the coloring composition is preferably 5 to 50 mass%, more preferably 10 to 40 mass%. By using this form, it is possible to obtain a colorant dispersion having good dispersibility and stability, and a coloring composition having good applicability and stability.

-additive-

The coloring composition of the present invention may contain various additives as required.

Examples of the additive include fillers such as glass and alumina; High molecular compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); Surfactants such as fluorine surfactants and silicone surfactants; Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like Adhesion promoters; Di-t-butylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4 (3-t-butyl-4-hydroxy-5-methylphenyl) propionyl] -1,1-dimethylethyl] -2,4,8,10-tetraoxa-spiro [5 5] undecane, thiodiethylene bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Antioxidants; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; An anti-aggregation agent such as sodium polyacrylate; Amino-1-pentanol, 3-amino-1,2-propane, 3-amino-1-pentanol, Diol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and the like; A developing agent such as mono [2- (meth) acryloyloxyethyl succinic acid], phthalic acid mono [2- (meth) acryloyloxyethyl], omega -carboxylic polycaprolactone mono (meth) .

The coloring composition of the present invention can be prepared by a suitable method. Examples of the method for producing the coloring composition of the present invention include those disclosed in Japanese Patent Laid-Open Nos. 2008-58642 and 2010-132874 have. When both the dye and the pigment are used as the coloring agent, as disclosed in JP-A-2010-132874, the dye solution is passed through the first filter, and the dye solution passed through the first filter is separately prepared A pigment dispersion or the like, and passing the resulting colored composition through a second filter. Further, it is also possible to dissolve the dye, the components (B) to (C), and other components to be used as necessary in a solvent, pass the obtained solution through the first filter, A method of mixing the obtained coloring composition with a pigment dispersion and passing the obtained coloring composition through a second filter may be adopted. Further, after the dye solution is passed through the first filter, the dye solution which has passed through the first filter is mixed with and dissolves the components (B) to (C) and other components to be used as required, A method in which the solution is passed through a second filter and further passed through a second filter is mixed with a separately prepared pigment dispersion and the resulting colored composition is passed through a third filter.

coloring Curing membrane  And a method for producing the same

The colored cured film of the present invention is formed using the coloring composition of the present invention, and specifically means each color pixel, a black matrix, a black spacer, etc. used in a display element or a solid-state image pickup element.

Hereinafter, a colored cured film used for a color filter and a method of forming the colored cured film will be described.

As a method of manufacturing a color filter, first, the following method can be mentioned. First, a light-shielding layer (black matrix) is formed on the surface of the substrate so as to partition a portion for forming a pixel as needed. Next, a liquid composition of the present invention radiation-sensitive coloring composition, for example, red is applied on the substrate, and then the substrate is pre-baked to evaporate the solvent to form a coating film. Subsequently, this coating film is exposed through a photomask, and then developed with an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, by post-baking, a pixel array in which red pixel patterns (colored cured films) are arranged in a predetermined arrangement is formed.

Subsequently, the respective radiation-sensitive coloring compositions were applied, pre-baked, exposed, developed, and post-baked in the same manner as above using each of the green-sensitive or blue-sensitive radiation sensitive coloring compositions to form a green pixel array and a blue pixel Arrays are sequentially formed on the same substrate. Thus, a color filter in which pixel arrays of three primary colors of blue, green, and red are arranged on a substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

The black matrix can be formed by forming a metal thin film of chromium or the like formed by sputtering or vapor deposition into a desired pattern by photolithography. By using a radiation-sensitive coloring composition in which a black pigment is dispersed, As shown in FIG.

Examples of the substrate used for forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.

These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum deposition, etc., if necessary.

When the radiation sensitive coloring composition is applied to a substrate, a suitable coating method such as a spraying method, a roll coating method, a rotation coating method (spin coating method), a slit die coating method (slit coating method) However, it is particularly preferable to employ a spin coating method or a slit die coating method.

Prebaking is usually carried out in combination with reduced pressure drying and heat drying. The reduced-pressure drying is usually carried out until 50 to 200 Pa is reached. The conditions for heating and drying are usually about 70 to 110 DEG C for about 1 to 10 minutes.

The coating thickness is usually 0.6 to 8 占 퐉, preferably 1.2 to 5 占 퐉, as a film thickness after drying.

Examples of the light source of radiation used when forming at least one kind selected from the pixels and the black matrix include a halogen lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, A lamp light source, and a laser light source such as an argon ion laser, a YAG laser, an XeCl excimer laser, or a nitrogen laser. As an exposure light source, an ultraviolet LED may be used. Radiation with a wavelength in the range of 190 to 450 nm is preferred.

The exposure dose of the radiation is generally preferably from 10 to 10,000 J / m < ² >.

Examples of the alkali developer include sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] 1,5-diazabicyclo- [4.3.0] -5-nonene and the like are preferable.

To the alkali developing solution, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added in an appropriate amount. After the alkali development, it is usually washed with water.

As the development treatment method, a shower development method, a spray development method, a dipping (immersion) development method, a puddle (liquid immersion) development method, or the like can be applied. The developing conditions are preferably 5 to 300 seconds at room temperature.

The post-baking condition is usually about 180 to 280 DEG C for about 10 to 60 minutes.

The film thickness of the thus formed pixel is usually 0.5 to 5 占 퐉, preferably 1.0 to 3 占 퐉.

As a second method for manufacturing a color filter, a method of obtaining pixels of respective colors by an inkjet method disclosed in Japanese Patent Laid-Open Nos. 7-318723 and 2000-310706 can do. In this method, a barrier wall serving also as a light shielding function is formed on the surface of a substrate. Subsequently, for example, a blue liquid composition of the present invention thermosetting coloring composition is ejected by an ink jet apparatus in a partition wall formed thereon, followed by prebaking to evaporate the solvent. Subsequently, this coating film is exposed, if necessary, and then post-baked to form a blue pixel pattern.

Then, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate by using each of the green or red thermosetting coloring compositions as described above. Thereby, a color filter in which three primary color pixel patterns of blue, green, and red are arranged on a substrate is obtained. However, the order of forming the pixels of each color in the present invention is not limited to the above.

In addition, the barrier ribs have a thicker film thickness than the black matrix used in the first method because they function not only to shield the light but also to prevent the thermosetting coloring composition of each color discharged in the compartment from being mixed. Thus, the barrier ribs are usually formed using a black radia radiation composition.

The substrate or radiation source used for forming the color filter, and the methods and conditions of prebaking and postbaking are the same as those of the first method. Thus, the film thickness of the pixel formed by the ink-jet method is about the same as the height of the partition wall.

After forming a protective film on the thus-obtained pixel pattern as necessary, a transparent conductive film is formed by sputtering. After a transparent conductive film is formed, a spacer may be further formed to form a color filter. The spacer is usually formed using a radiation sensitive composition, but it may also be a spacer (black spacer) having light shielding properties. In this case, a coloring and radiation-sensitive composition in which a black coloring agent is dispersed is used, but the coloring composition of the present invention can be suitably used for forming such a black spacer.

The coloring composition of the present invention can be suitably used for the formation of any colored cured film such as each color pixel, black matrix, and black spacer used in the color filter.

The color filter including the colored cured film of the present invention thus formed is very useful for a color liquid crystal display element, a color image pickup tube element, a color sensor, an organic EL display element, an electronic paper, and the like because of its extremely high luminance and tinting power. Further, the display element described later may be one having at least one colored cured film formed using the coloring composition of the present invention.

Display element

The display element of the present invention comprises the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and an electronic paper.

The color liquid crystal display device comprising the colored cured film of the present invention may be of a transmissive type or a reflective type, and a suitable structure may be adopted. For example, a structure in which a color filter is formed on a substrate different from a substrate on which a thin film transistor (TFT) is disposed, and a substrate on which a driving substrate and a color filter are formed faces each other through a liquid crystal layer , A substrate on which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (indium tin oxide) electrode or an IZO (mixture of indium oxide and zinc oxide) A structure in which the substrate faces the liquid crystal layer may be adopted. The latter structure can remarkably improve the aperture ratio and has an advantage that a bright and high-precision liquid crystal display element can be obtained. When adopting the latter structure, the black matrix or the black spacer may be formed on either the substrate on which the color filter is formed or the substrate on which the ITO electrode or the IZO electrode is formed.

The color liquid crystal display device having the colored cured film of the present invention may have a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). Examples of white LEDs include white LEDs that combine red LEDs, green LEDs, and blue LEDs to obtain white light by mixing colors, white LEDs that combine blue LEDs, red LEDs, and green phosphors to obtain white light by mixing colors, A white LED that obtains white light by mixing a red light emitting phosphor and a green light emitting phosphor, a white LED that obtains white light by mixing a blue LED and a YAG phosphor, a blue LED, an orange light emitting phosphor, and a green light emitting phosphor, A white LED for obtaining white light, an ultraviolet LED, a white LED for obtaining a white light by mixing a red light emitting phosphor, a green light emitting phosphor and a blue light emitting phosphor in combination, and the like.

The color liquid crystal display device having the colored cured film of the present invention may be applied to a color liquid crystal display device such as a twisted nematic (TN) type, a super twisted nematic (STN) type, an in-plane switching (IPS) type, a vertical alignment (VA) type, an optically compensated birefringence ) Type liquid crystal mode can be applied.

Further, the organic EL display device having the colored cured film of the present invention can have a suitable structure, for example, a structure disclosed in Japanese Patent Laid-Open No. 11-307242.

Further, the electronic paper having the colored cured film of the present invention can have a suitable structure, and for example, there is a structure disclosed in Japanese Patent Laid-Open No. 2007-41169.

[Example]

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

(Synthesis of the present colorant)

Synthesis Example 1

0.28 parts by mass of a compound represented by the following formula (a-1) synthesized according to the method described in JP-A-2011-148994 was dissolved in 5 parts by mass of dimethylformamide, and tris (acetylacetonato) iron (III ) And 0.16 parts by mass of sodium acetate were added and the mixture was heated and stirred at 135 占 폚 for 24 hours. The reaction solution was poured into a 30% by mass aqueous solution of 20% sodium chloride, and the precipitated solid was filtered, washed with a small amount of pure water, and dried at 60 캜 under reduced pressure to obtain a compound represented by the following formula (a-2) 0.27 parts by mass.

0.12 parts by mass of the compound represented by the formula (a-2) and 0.052 parts by mass of rhodamine 6G as a xanthene-based dye were dissolved in 1 part by mass of N-methylpyrrolidone and stirred for 5 hours. The reaction solution was poured into 20 parts by mass of water, and the resulting solid was filtered and dried at 60 DEG C under reduced pressure to obtain 0.13 parts by mass of a compound represented by the following formula (A2). This is referred to as colorant (A2).

Synthesis Examples 2 to 5

Colorants (A3) to (A6) were synthesized in the same manner as in Synthesis Example 1, except that the kinds of metal complexes and / or basic dyes used as starting materials in Synthesis Example 1 were changed as shown in Table 1.

CI Basic Red 12 is a compound represented by the following formula.

≪ Preparation of colorant solution >

Production Example 1

5 parts by mass of Basic Violet 11: 1 represented by the following formula and 95 parts by mass of cyclohexanone as a solvent were mixed to prepare a colorant solution (A1).

Production Example 2

, 5 parts by mass of the colorant (A2) and 95 parts by mass of cyclohexanone as a solvent were mixed to prepare a colorant solution (A2).

Production Examples 3 to 6

Colorant solutions (A3) to (A6) were prepared in the same manner as in Production Example 2 except that the colorants (A3) to (A6) were used instead of the colorant (A2)

≪ Synthesis of binder resin >

Synthesis Example 6

To a flask equipped with a cooling tube and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was charged and replaced with nitrogen. The mixture was heated to 80 占 폚 and, at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate , 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 2,2'-azobis (2,4- 6-pyrrolidone) was added dropwise over 1 hour, and the mixture was polymerized at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 占 폚 and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The resulting binder resin had Mw of 12,200 and Mn of 6,500. This binder resin is referred to as " binder resin (B1) ".

≪ Preparation and evaluation of colored composition >

Preparation of coloring composition

Example 1

40.5 parts by mass of the colorant solution (A1) as colorant, 3.0 parts by mass of the colorant solution (A2) as the colorant, 26.3 parts by mass of the binder resin (B1) solution as the binder resin, (C) 9.9 parts by mass of a mixture of hexaacrylate and dipentaerythritol pentaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Kabushiki Kaisha), 2-benzyl-2-dimethylamino-1- (4-morpholino (Trade name: IRGACURE 369, manufactured by Ciba Specialty Chemicals) and 0.1 part by mass of NCI-930 (manufactured by Adeka Kabushiki Kaisha) as a fluorinated surfactant, and Megaface F-554 Ltd.) and 0.05 part by mass of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a colored composition (S-1) having a solid content concentration of 20 mass%.

Evaluation of contrast

The obtained coloring composition was coated on a glass substrate using a spin coater and then prebaked on a hot plate at 80 캜 for 10 minutes to form a coating film. The number of revolutions of the spin coater was changed and three coating films having different film thicknesses were formed by the same operation.

Subsequently, after cooling the substrate to room temperature, each coating film was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 2,000 J / m ² without using a photomask using a high-pressure mercury lamp. Subsequently, a developer containing 0.04 mass% potassium hydroxide aqueous solution at 23 캜 was ejected onto these substrates at a developing pressure of 1 kgf / cm ² (nozzle diameter: 1 mm) to perform showering for 90 seconds. Thereafter, this substrate was cleaned with ultrapure water, air-dried, and post-baked in a 200 ° C clean oven for 30 minutes to form a cured film for evaluation.

The substrate on which the cured film was formed was sandwiched between two polarizing plates and the front polarizing plate was rotated while being irradiated with fluorescent light (wavelength range of 380 to 780 nm) from the back side to measure a luminance meter LS-100 (manufactured by Minolta Co., Ltd.) And the maximum and minimum values of the light intensity transmitted by the light source were measured. For each of the cured films, a value obtained by dividing the maximum value by the minimum value was defined as a contrast ratio. From the measurement results, the contrast ratio at the chromaticity coordinate value y = 0.080 was determined. The evaluation results are shown in Table 2. Further, the contrast ratio means that the larger the value is, the better.

Examples 2 to 5

(S-2) to (S-5) were prepared in the same manner as in Example 1 except that the colorant solution shown in Table 2 was used instead of the colorant solution (A2) The obtained coloring composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

Comparative Example 1

A coloring composition (S-6) was prepared in the same manner as in Example 1 except that the colorant solution (A2) was not used. The obtained coloring composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

Claims (7)

(A) a colorant, (B) a binder resin, and (C) a polymerizable compound,
Wherein the colorant comprises a salt of a cation having a xanthene skeleton or a cation having a methine skeleton and an anion of a metal complex,
Wherein the metal constituting the metal complex is at least one selected from the group consisting of iron, nickel, copper and aluminum. The coloring composition according to claim 1, wherein the anion of the metal complex has an azo compound in the ligand. 3. The coloring composition according to claim 1 or 2, wherein the anion of the metal complex having the azo compound in the ligand is an anion represented by the following chemical formula (4).

[In the formula (4)
The ring Z < ⁵ > independently represents a substituted or unsubstituted heterocyclic group,
The ring Z ⁶ represents an aromatic hydrocarbon group which is substituted or unsubstituted independently of each other,
M ¹ represents iron, nickel, copper or aluminum,
t ¹ and t ² independently represent 0 or 1] The coloring composition according to any one of claims 1 to 3, wherein the cation having the xanthene skeleton is a cation represented by the following formula (1).

[In the formula (1)
R ^1, R ^2, R ³ and R ⁴ are independently a hydrogen atom, -R ⁸ or a carbon number of 6 to 10 are shown a group of the aromatic hydrocarbon, the hydrogen atoms contained only the aromatic hydrocarbon groups include a halogen atom, -R ⁸ each other, -OH, -OR ⁸ , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ R ⁸ , -SO ₂ NHR ⁹ or -SO ₂ NR ⁹ R ¹⁰ There may be,
R ⁵ and R ⁶ independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
R ⁷ represents -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ R ⁸ , -SO ₂ NHR ⁹ or -SO ₂ NR ⁹ R ¹⁰ ,
r represents an integer of 0 to 5, and when r is an integer of 2 or more, plural R ^{7 s} may be the same or different,
R ⁸ represents a saturated hydrocarbon group having 1 to 20 carbon atoms, provided that the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and an oxygen atom, a carbonyl group or -NR ⁸ - may be interposed between the CC bonds of the saturated hydrocarbon group Lt; / RTI >
R ⁹ and R ¹⁰ independently represent a straight chain alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Z, or a substituted or unsubstituted C 2 -C 10 arylene group formed by bonding R ⁹ and R ¹⁰ to each other. Provided that the hydrogen atoms contained in the alkyl group and the cycloalkyl group may be substituted with a hydroxyl group, a halogen atom, -Z, -CH = CH _2, or -CH = CHR ⁸ , May have an oxygen atom, a carbonyl group or -NR ⁸ - between the CC bonds of the cycloalkyl group, and the hydrogen atom contained in the heterocyclic group may be substituted with -R ⁸ , -OH or -Z,
M represents a sodium atom or a potassium atom,
Z represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 4 to 10 carbon atoms, provided that the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is -OH, -R ⁸ , -OR ⁸ , - NO ₂ , -CH = CH ₂ , -CH = CHR ^8, or may be substituted with a halogen atom) The coloring composition according to any one of claims 1 to 4, wherein the cation having a methine skeleton is a cation represented by the following formula (2) or (3).

[In the formula (2)
R ²¹ to R ²⁶ independently represent a hydrogen atom or an alkyl group,
The ring Z ¹ and Z ² independently represent an aromatic ring, and the hydrogen atom contained in the aromatic ring may be a halogen atom, a nitro group, an alkyl group having 1 to 8 carbon atoms, a fluorinated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms , An alkylcarbonyl group having 2 to 6 carbon atoms,
and g represents an integer of 1 to 4)

[In the formula (3)
R ²⁷ to R ³⁰ independently represent a hydrogen atom or an alkyl group,
The ring Z ³ and Z ⁴ independently represent an aromatic ring, and the hydrogen atom contained in the aromatic ring may be a halogen atom, a nitro group, an alkyl group having 1 to 8 carbon atoms, a fluorinated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms , An alkylcarbonyl group having 2 to 6 carbon atoms,
Q represents an oxygen atom or a sulfur atom,
h represents an integer of 1 to 4] A colored cured film formed using the coloring composition according to any one of claims 1 to 5. A display device comprising the colored cured film according to claim 6.